Gellan gums were characterised for the first time using free-solution capillary electrophoresis (CE) or CE under critical conditions (CE-CC). CE-CC is a fast method that separates the polysaccharide. Gellan gums are shown to be heterogeneous in terms of their electrophoretic mobility at 55°C revealing: oligomer peak(s), broad peaks of polymers with a random coil conformation with different degrees of acylation (composition), aggregates, and polymers with double-helix conformation. CE-CC is complementary with the rheological analysis also performed in this work. Sonication of gellan gums is shown to decrease the viscosity of gellan gum mainly by breaking up aggregates. The effect of sonication is stronger on the high-acyl gellan gum since the latter has a far higher tendency to aggregate.